EP0711744B1 - Method for making acyl substituted resorcinols - Google Patents

Method for making acyl substituted resorcinols Download PDF

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Publication number
EP0711744B1
EP0711744B1 EP95307549A EP95307549A EP0711744B1 EP 0711744 B1 EP0711744 B1 EP 0711744B1 EP 95307549 A EP95307549 A EP 95307549A EP 95307549 A EP95307549 A EP 95307549A EP 0711744 B1 EP0711744 B1 EP 0711744B1
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EP
European Patent Office
Prior art keywords
resorcinols
substituted resorcinols
acyl substituted
making
accordance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95307549A
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German (de)
English (en)
French (fr)
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EP0711744A1 (en
Inventor
James Edward Pickett
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
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General Electric Co
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Publication date
Application filed by General Electric Co filed Critical General Electric Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions

Definitions

  • This invention relates to a novel method for making acyl substituted resorcinols. More particularly, the instant invention is directed to a method for making acyl substituted resorcinols by contacting resorcinols and acid halides in the presence of catalytic amounts of transition metal Lewis acids.
  • Thermoplastic resins are generally characterized by their many advantageous properties which include optical clarity, high ductility, high heat deflection temperature as well as dimensional stability. As a result of such properties, they are often employed in many commercial applications.
  • thermoplastic resins possess the above-described advantageous properties, they often display low abrasion and chemical solvent resistances, and like many other organic polymeric materials, they are susceptible to photodegradation by ultraviolet light. The photodegradation typically results in unfavorable characteristics including yellowing and erosion of the resin surface.
  • Diacyl resorcinols particularly dibenzoyl resorcinols, have been found to be effective light stabilizers in polymer resins.
  • dibenzoyl resorcinols are prepared by treating dimethoxybenzene with benzoyl chloride in the presence of at least stoichiometric amounts of anhydrous aluminum chloride in an organic solvent.
  • such a method is not very favorable, since among other reasons, it results in the release of environmentally unfriendly organic volatiles and requires disposal of large amounts of excess aluminum chloride as well as by-products thereof.
  • the instant invention is directed to a novel method for making acyl substituted resorcinols while minimizing environmentally unfriendly side effects.
  • dibenzoyl resorcinols are prepared by subjecting dialkyl ethers to acyl chlorides and at least stoichiometric amounts of aluminum chloride and the use of resorcinols as a starting material is discouraged.
  • dibenzoyl resorcinol is prepared via the photochemical Fries rearrangement of resorcinol dibenzoate to a benzoate ester of 2,4-dihydroxy benzophenone and subsequently dibenzoyl resorcinol.
  • the instant invention is patentably distinguishable from the above-described, since among other reasons, it is directed to a novel method for making acyl substituted resorcinols by contacting resorcinols and acid halides in the presence of catalytic amounts of transition metal Lewis acids.
  • DE-A-2616479 discloses substituted fluoroacyl resorcinols prepared by reacting a resorcinol compound with a compound of the formula R 1 COY where R 1 is a perfluoroalkyl group and Y is hydroxyl, amino, acyloxy or halogen in the presence of a Friedel Crafts catalyst and a solvent.
  • JP-A-61180738 discloses acyl substituted resorcinols wherein the acyl group is a C 1-5 aliphatic group obtained by reacting resorcinol with a carboxylic acid halide in the presence of zinc halide and an inert solvent.
  • the present invention is directed to a novel method for making diaroyl substituted resorcinols, said method comprises the step of melt reacting:
  • R 1 is preferably a benzoyl group and the preferred resorcinols employed in the instant invention are 1,3-dihydroxybenzene and 2,4-dihydroxy-benzophenone.
  • A is preferably a phenyl group and X is preferably chlorine.
  • the catalyst employed is a transition metal Lewis acid and the resulting product obtained in the instant invention is an acyl substituted resorcinol and preferably 4,6-dibenzoylresorcinol.
  • transition metal Lewis acids employed include cadmium chloride and iron chloride.
  • the most preferred transition metal Lewis acid employed in this invention is zinc chloride.
  • the instant novel method reveals many new and unexpected results which include the discovery that catalytic amounts of transition metal Lewis acids may be employed when resorcinols are subjected to and reacted with acid halides to afford acyl substituted resorcinols and particularly 4,6-diacyl substituted resorcinols.
  • the reaction occurs in a single step and does not require the use of organic solvents for acyl substituted resorcinol formation since such a reaction takes place in the melt.
  • R 1 is not an acyl group, diacyl substitutions are unexpectedly observed.
  • this invention comprises the step of contacting resorcinols and acid halides in the presence of catalytic amounts of transition metal Lewis acids to produce a reaction mixture.
  • the reaction mixture is typically heated to a temperature in the range of 120°C to 250°C and preferably in the range of 150°C to 220°C and most preferably in the range of 170°C to 220°C. Additionally, it is noted herein that heating may begin prior to, during or after the reactants and catalyst are combined.
  • the amount of transition metal Lewis acid (catalyst) required in the instant invention is not stoichiometric and is 0.1 to 50.0 mole percent and preferably 1.0 to 30.0 mole percent and most preferably 5.0 to 15.0 mole percent based on total moles of resorcinol employed. Additionally, about 2 moles of acid halide are employed for every mole of resorcinol employed when R 1 is not an acyl group and about 1 mole of acid halide is employed for every mole of resorcinol when R 1 is an acyl group.
  • reaction mixture Once the reaction mixture is obtained, an esterification occurs and the resorcinols are converted to ester intermediates. The ester intermediates then subsequently and spontaneously rearrange to form the desired acyl substituted resorcinols in the reaction product. Further, it is within the scope of the instant invention to recrystallize the reaction product with organic solvents in order to obtain substantially pure acyl substituted resorcinols. Often, the product obtained after work-up is at least about 95% pure.
  • acyl substituted resorcinols obtained may be confirmed via conventional techniques including proton and carbon-13 nuclear magnetic resonance spectroscopy, infrared spectroscopy and GLC analysis.
  • a 100 mL round-bottomed flask equipped with a magnetic stirring bar, gas scrubber and oil bath heater at 120°C was charged with 0.54g (4 mmol) of anhydrous zinc(II) chloride (5 mole percent based on total resorcinol) and 19.0 mL (164 mmol) of benzoyl chloride to produce a catalyst mixture.
  • 8.80g (80 mmol) of 1,3-dihydroxybenzene was added to the catalyst mixture in portions over several minutes to produce a reaction mixture. The temperature was then raised to about 205°C over the course of 20 minutes and held at that temperature for 1 hour. A sample of the reaction mixture was removed for NMR spectroscopy.
  • Results showed approximately 60% conversion to 4,6-dibenzoyl resorcinol.
  • the reaction mixture was cooled to 120°C and 40 mL of glacial acetic acid were added.
  • the reaction mixture was further cooled to 80°C and 20 mL of absolute ethanol were added.
  • the resulting mixture was transferred to a beaker and allowed to cool to 5°C in a refrigerator.
  • a solid was recovered via filtration, washed with about 50 mL of cold ethanol and dried to give orange plates of 4,6-dibenzoyl resorcinol (11.80g 46% yield). Recrystallization from a mixture of 50 mL of ethanol and 15 mL chlorobenzene gave 10.8g (42% yield) of pale yellow 4,6-dibenzoyl resorcinol.
  • Example 2 was prepared in a manner similar to the one described in Example 1 except that 2,4-dihydroxybenzophenone was employed in lieu of 1,3-dihydroxybenzene and 82 mmol of benzoyl chloride were used and 10 mole percent of anhydrous zinc(II) chloride was used based on total resorcinol. 10.6g (42%) of substantially pure 4,6-dibenzoyl resorcinol was recovered after recrystallization.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP95307549A 1994-11-08 1995-10-24 Method for making acyl substituted resorcinols Expired - Lifetime EP0711744B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/336,135 US5567850A (en) 1994-11-08 1994-11-08 Method for making acyl substituted resorcinols
US336135 1999-06-18

Publications (2)

Publication Number Publication Date
EP0711744A1 EP0711744A1 (en) 1996-05-15
EP0711744B1 true EP0711744B1 (en) 2000-04-05

Family

ID=23314728

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95307549A Expired - Lifetime EP0711744B1 (en) 1994-11-08 1995-10-24 Method for making acyl substituted resorcinols

Country Status (8)

Country Link
US (1) US5567850A (enExample)
EP (1) EP0711744B1 (enExample)
JP (1) JP3884784B2 (enExample)
CN (1) CN1067371C (enExample)
DE (1) DE69516083T2 (enExample)
ES (1) ES2144580T3 (enExample)
SG (1) SG63524A1 (enExample)
TW (1) TW317563B (enExample)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5981073A (en) * 1997-01-16 1999-11-09 General Electric Company Compounds based on dibenzoylresorcinol, and related compositions and articles
KR100453590B1 (ko) * 2001-10-17 2004-10-20 주식회사 바이오랜드 벤젠 디올의 모노카르보닐화 방법
CN100439307C (zh) * 2003-07-08 2008-12-03 荷兰联合利华有限公司 化妆活性物质的制备方法
CN103159608A (zh) * 2011-12-14 2013-06-19 南京华狮化工有限公司 一种间苯二酚烷基酮的制备方法
CN107879910B (zh) * 2017-11-02 2021-06-11 武汉科技大学 一种2,4-二羟基二苯甲酮的绿色合成工艺

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2794052A (en) * 1957-05-28 Process for the preparation of diacyl
US1750299A (en) * 1925-04-16 1930-03-11 Sharp & Dohme Inc Production of acyl resorcinols
US2891996A (en) * 1956-04-23 1959-06-23 Dow Chemical Co 2, 4-dihydroxy benzophenone derivatives
US3769349A (en) * 1967-01-27 1973-10-30 Kyodo Chem Co Ltd Process for preparing 2,4-dihydroxybenzophenones
US3526666A (en) * 1968-01-12 1970-09-01 Ferro Corp Synthesis of 2-hydroxy-4-alkoxybenzophenones
DE2616479C2 (de) * 1976-04-14 1986-12-04 Brickl, Rolf, Dr., 7951 Warthausen Substituierte Fluoracylresorcine, Verfahren zu ihrer Herstellung und diese enthaltende Arzneimittel und Kosmetika
DE2963903D1 (en) * 1978-12-05 1982-11-25 Fisons Plc A process for the production of 2-alkyl- or 2-alkenyl-4,6-diacetyl resorcinols; 2-allyl-4,6-diacetyl resorcinol
JPS61180738A (ja) * 1985-02-06 1986-08-13 Nippon Zeon Co Ltd アルキル（ジヒドロキシフエニル）ケトンの製造法
DE3904371A1 (de) * 1989-02-14 1990-08-16 Basf Ag Verfahren zur herstellung von 2,4-dihydroxybenzophenon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.MARCH: "ADVANCED ORGANIC CHEMISTRY", MCGRAW-HILL, 2ND ED *

Also Published As

Publication number Publication date
ES2144580T3 (es) 2000-06-16
CN1131656A (zh) 1996-09-25
SG63524A1 (en) 1999-03-30
JPH08245488A (ja) 1996-09-24
TW317563B (enExample) 1997-10-11
JP3884784B2 (ja) 2007-02-21
US5567850A (en) 1996-10-22
CN1067371C (zh) 2001-06-20
DE69516083D1 (de) 2000-05-11
DE69516083T2 (de) 2000-09-14
EP0711744A1 (en) 1996-05-15

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